Polymerization of α-methylstyrene by n-butyllithium in tetrahydrofuran

✍ Scribed by Bitsenko, M. I. ;Podolsky, A. F. ;Khvostik, G. M. ;Sokolov, V. N.

• Publisher: Wiley (John Wiley & Sons)
• Year: 1972
• Tongue: English
• Weight: 502 KB
• Volume: 10
• Category: Article
• ISSN: 0449-296X
• DOI: 10.1002/pol.1972.170101108

✦ Synopsis

Abstract

The kinetics of polymerization of α‐methylstyrene by n‐BuLi (labeled with C^14^ and unlabeled) has been studied in tetrahydrofuran at −78°C. The catalyst n‐BuLi was used as a complex of n‐BuLi in THF and a hexane solution of n‐BuLi. Contrary to expectations, the relative polymerization rate and the catalyst consumption were higher when a hexane solution of n‐BuLi was used. Experimental molecular weights of the polymers greatly exceeded those calculated for the case of complete catalyst consumption. The polymers exhibited low polydispersity, and when a hexane solution of n‐BuLi was used, the molecular weight distribution was bimodal. The rate of initiation for the case of polymerization α‐methylstyrene with a hexane solution of n‐BuLi as a catalyst was much higher than in the polymerization of α‐methylstyrene with the use of the complex of n‐BuLi in THF as in situ catalyst. Experimental data confirm the preferable interaction of α‐methylstyrene with associated n‐BuLi in the presence of THF. The complex which was formed as a result of such interaction is an active centers of polymerization.